Removing water from brine



April 25, v H555 REMOVING WATER FROM BRINE Filed Sept. 1G, 1963 ku@ s@ JY :LUHP

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1United States Patent 3,316,172 REMVING WATER FRUM BRINE Howard V. Hess, Glenham, NY., assignor to Texaco Inc., New York, N .Y., a corporation of Delaware Filed Sept. 16, 1963, Ser. No. 310,515 19 Claims. (Cl. 210-59) This application is a contnuation-in-part of my copending patent application, Ser. No. 144,240, tiled Oct. 10, 1961, now abandoned.

The present invention relates to a novel process and apparatus for separating fresh Water from brine. The process is applicable to the lrecovery of salt-free Water from brines and to the concentration of various brines for the recovery of inorganic compounds contained therein.

In one of its more specific aspects, the present invention is concerned with a process for separating water from brine wherein a hot hydrocarbon liquid under pressure is brought into contact with heated brine to form a from inorganic compounds with water from the brine, separation of the complex from the residual brine, decomposition of the complex into its constituents. The term brine is used in a .broad sense to denote the entire range of concentrations -of water soluble inorganic compounds in water, for example, natural sal-ine water containing sodium chloride, including brackish water, sea water, and saturated or nearly saturated brines, such as the brine in Great Salt Lake or brines obtained from wells. In addition to sdium chloride-containing solutions, other brines to which the process may be applied include aqueous solutions of dissolved mineral salts, for example, halides, carbonates and sulfates of sodium, potassium, lithium, calcium, magnesium, zinc and copper.

The present invention involves a novel desalination process which is dependent upon contact of hot brine with i a hot hydrocarbon liquid characterized by the property t of extracting a greater amount perature (e.g., at a temperature ofA 500 F. 'or above) A-than at a lower temperature, whereby water is extracted from the brine by the hydrocarbon and forms a complex of water at a high temtemperat'ure to cause rthe hydrocarbon and water to separate lfrom one another as two liquid phases; the water phase or the residual brine may be product and the hydrocarbon phase is recycled to the extraction zone.

.The term complex is used herein to designate the lsolution lof water in hydrocarbon liquid, especially the extract leaving the extraction zone, since it is not entirely it is a true solution of water in hydrocarbon liquid or a hydrocarbon solution containing a hydrate of the water and hydrocarbon.

For greatest eiciency the present process should be operated at a temperature above 500 F. for the extracafter which the temperature is reduced below the extraction temperature for the phase separation step, advantageously by at least 50 below the extraction temperature to assure 'breaking out the major part of the water. When using aliphatic hydrocarbons, somewhat greater extraction eiiiciency is obtained if the temperature is kept above 550 F.

By Way of illustration, n-decane has the property of extracting 22.2% its weight of Water at 575 F., 9% at 550 F., and only 3.3% at 500 F. Consequently, with the extraction process operating at 575 F., and the decomposition step at 500 F., there is a recovery of water in the amount of about 19% of the n-decane.

1s formed and accumulates in pinene, etc.;

The operating pressure of the extraction step must bt sufficiently high to maintain both the brine and the hy bons of 8 to 20 carbon atoms,

Examples of individual hydrocarbon types which can be used in octanes, isoocatane, nonanes, decanes, propylene tetramer, hexadecane, 2methyllpentene etc.; naphthenic hydrocarbons, eg., methylcyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, ethylcyclohexane, tetralin, isopropylcyclohexane, cyclohexene,

and aromatic hydrocarbons, eg., benzene, cumene, xylenes, methylnaphthalenes, etc.

Preferred petroleum fractions useful in the present 10 to 12 carbon atoms per molecule; isoparaliin hydrocarbons of 12 carbon atoms per molecule, eg., the bottoms fraction obtained from alkylation of butylenes with isobutane; Udex extract, an aromatic hydrocarbon fraction consisting essentially of hydrocarbons of 9 to 10 Carbon atoms per molecule obtained on extraction of petroleum naphtha with a mixture of diethylene glycol and water; propylene tetramer; gasoline fraction hydrocarbons of 10 to 12 carbon atoms per molecule; and naphthenes containing 9 to l0 carbon atoms per molecule.

In the drawings:

FIGS. 1 and 2 are schematic flow diagrams showing simple arrangements of apparatus for performing the invention by co-current ow operation, and by countercurrent operation, respectively.

Referring to FlG. 1, brine and hydrocarbon liquid are fed at a high pressure such as 2000 p.s.i.g. into the bottom of a long narrow pipe.1, in the lower portion of which the temperature is maintained at a high value such as above 550 F. by a surrounding electric heater, whereupon a complex of salt-free Water with the hydrocarbon an unheated upper portion of the pipe. This complex flows out the top and through a heat exchanger 2 wherein its temperature is reduced well below 550 F., for example, to atmospheric temperatute, to decompose the complex and form a water phase and a hydrocarbon phase. The stream then passes through a pressure reducer 3 wherein pressure is reduced to atmospheric, and enters a collecting vessel 4.

Instead of feeding makeup brine to extractor 1, a batch of brine may be extracted, with its level gradually dropping and its salt content increasing.

Product water containing less than p.p.m. salt was obtained by treating 500 cc. batches of real and synthetic inches of berl saddles, using the apparatus shown in FIG. 1. Makeup sea water in an amount equal to produ-ct water was added in some examples as indicated. Separa- 4 on Was accomplished by cooling the extract to room be useful for most industrial processes. However, pozmperature. Conditions are set forth in Table I below: tability is assured by passing the water through an absorber TABLE i Extractor HC Water Vol. Percent* Hydrocarbon Rate, Product, Water in cc./lir. Temp., Pres., cc./hr.* Extract F. p.s.i.g.

i- )dorloss spirits 601 625 2, 500 b 165 21. 5 (erosene 600 630 2,100 n 230 27. 8 D0. 150 500 800 0. 5 4. a Jumene. 600 625 2,100 b d 335 35. 9 Xyiene 300 500 2, 000 20 6. 7 Do 300 575 2,000 35 11.0 Do 300 625 2,100 72 24. 0 Do 300 040 2, 050 08 32. G

" Averages:

Alkylation bottoms: C12 plus isomerie parains. b Equivalent amount of SW added. u 15 hour period. d 1G hour period. The improvement effected by increasing temperature 43 Icontaining an adsorbent such as activated carbon which is illustrated above, o-xylene, showing a S-fold increase in adsorbs hydrocarbon impurities. i product when operating at 640 F. as compared to 500 F. The upper layer 45 of separated hydrocarbon is passed Referring to FIG. 2, there is shown a continuous exl through a conduit 47, pump 49, and heater 25 back into tractor 11 comprising a central column 13 comprising an the extractor 11 for reuse in the process. Makeup hydroextractiori Zone surrounded by a jacket through which carbon is added through a supply line 51 as needed. hot gases may be passed, if desired, or which can be filled Product water containing less than 100 p.p.m. salt was with a heat insulating material, alternatively. Jacket 15 obtained by countercurrent extraction of sea water (SW) also may be used for cooling where the heat of solution containing about 3% salt in an unpacked extractor 11/2 is such that temperature tends to rise too high. inches inside diameter and 60 inches long. Separation Brine from a supply line 17 is passed at a high pressure was accomplished by cooling to room temperature. Pressuch as 200 p.s.i.g. through a heater 19 wherein its temsure was reduced to atmospheric, and there was no reperature is raised to a high level such as 600 F. Without cycle of hydrocarbons. Conditions are set forth in Table vaporization, and is then passed into the upper half of H below:

TABLE 1I Extractor Products no sw Hydrocarbon Rate, Rate,

ce/lir. cc./lir. Temp., Pres., Water, Brine, F. p.s.i.g. cc./hr. cc./hr. J Benzene 3,000 520 500 1,800 430 Cuinene. 000 230 540 2, 000 151 85 o-Xylene 1, 000 460 575 2, 850 360 100 Odoi'less spirits 1 3, 250 422 584 2, 000 364 5S n-Decane, 50% n-Uiidecane l, 550 420 611 2, 500 378 42 1 Alkylation bottoms: C12 plus isomeric parafins. column 13 at a point near its top so as to ow downward- Norwalk sea water containing about 3% salt was exly and then out the bottom through a discharge conduit tracted with methylcyclohexane in an unpacked tower hav- 21. The leaving brine is quite concentrated, containing ing an inside diameter of 11/2 inches and .a length of 72 as much as 10-20% salt. inches.

A suitable hydrocarbon, such as kerosene, is passed at The following table lists the conditions and results. a similarly high pressure by way of a -conduit 23 through TABLE iiifCoN'riNUoUs EXTRACTroN oF FnEsli-i a second heater 25 wherein its temperature is raised to a WATER FROM -SEA WATER WITH METHYLCYCLO- high level such as 630 F., after which it is passed into the HEXA-NE IN A 11/2 X 72 TOWER lower half of column 13 near its bottom and, due to its o 575 Temp., F. A lower specific gravity than brine, ows upwardly 1n 60 pressures ps i g 200() ycountercurrent direct contact with the downwardly flow- Charge ftes. jing brine. As the two liquids pass in contact with one MCH C( /hr 585 another, a complex of hydrocarbon and water (which is Sea Water cjr 124 :substantially free from salt) is formed and, due to its Duration hr 25 .lower gectl gravlty thn the 12mg actclnjuiate 11n tthe 65 Vol. percent water in extract 13.65 Space a le top O CO umn a Ove e une me Vol, percent fresh water extracted 51.3

The complex ilows out the top of column 13 through a Vconduit 29 and passes through a cooler 31 to eifect phase The PIOCGSS dreflbd 111 COHHCUOD Wlh FIGS 1 2 separation, and then into a separator 33. can be operated with either the brine or the hydrocarbon In the separator 33 there is formed a body of liquid 70 lquld aS the COBUHQOUS Phase- 1S PM ClllaY Hdl/an comprising a lower phase 39 which is almost pure water, igeOUS i0 Operai@ With the hYdf0Cafb0n-1lqu1d 3S the COD' and an upper phase 45 which is almost pure liquid hydro- UHUOUS Phasf becaue SCjlle accumulatlon (from C3504 carbon. The water is drawn off the bottom through a and M2304 111th@ brule) 1S PfCVefled, and because COTTO- Onduit 41 and recovered as product, Ordinarily this Sion of metal is reduced when tne metal walls are wet 'water is tree enough from hydrocarbon impurity so as to 75 with hydrocarbon.

On the other hand, superior heat exchange is obtained when the continuous phase liquid is that liquid which is used in smaller volume, which is usually the brine; (this is because there are formed more bubbles of the larger volume liquid than bubbles of the smaller volume liquid in the reverse arrangement).

While the invention has been described its primary object the recovery of salt-free water from brine, it is evident that the highly concentrated brine leaving the `bottom of the value and may be the primary product of or a valuable by-product. Brines contain sodium chloride and often contain such other commercially valuable salts, such as magnesium, bromine and iodine salts which may be extracted from the concentrated brine product of the process.

I claim:

1. A process for extracting water from brine cmprising bringing into contact with one another in an extraction zone hot brine and a hot hydrocarbon liquid consisting essentially of hydrocarbons containing not less than 6 and not more than 30 carbon atoms per molecule characterized by the ability to extract more water at a high temperature than at a lower temperature thereby extracting water into said hydrocarbon liquid and forming a complex therewith, removing said complex from contact with residual brine, cooling said complex to form a water phase and hydrocarbon phase, and separating said water phase from said hydrocarbon phase,

2. A process in accordance with claim 1 wherein the operating pressure is suthciently high to maintain said brine, said `water and said hydrocarbon liquid in liquid phase.

above with the process with said brine as said hot hydrocarbon liquid.

4. A process according to `claim 1 wherein said hydrocarbon liquid is maintained as a continuous phase in said contacting Zone.

5. A process according to claim 1 wherein said brine is present as a continuous phase in said contacting zone.

6. A process in accordance with claim 1, also comprising removing any residual hydrocarbon liquid from said recovered water phase.

7. A process in accordance with claim 2, wherein said hot brine and said hot hydrocarbon liquid are at an extraction temperature above 500 F. 'but below the apparent critical temperature of said hydrocarbon and wherein the temperature of said complex is reduced at least 50 below said extraction temperature to eiect said phase separation.

8. A process in accordance with claim 7 wherein the pressure is above 1000 p.s.i.g.

9. A process in accordance with claim 1 wherein said hydrocarbon liquid and said brine are supplied as flowing streams to said extraction zone.

10. A process in accordance with claim 9 wherein said hydrocarbon liquid and said ybrine iow Itto-currently in said extraction zone.

1l. A process in accordance with claim 9 wherein said hydrocarbon liquid and said brine ows countercurrently in said extraction Zone.

12. A process according to claim 1 wherein said hydrocarbon liquid consists essentially of isoparaflin hydrocarbons of at least l2 carbon atoms per molecule obtained as bottoms from the alkylation of butylenes with isobutane.

13. A process according to claim 1 wherein said hydrocarbon liquid consists essentially of hydrocarbons containing not less than l() and not more than l2 carbon atoms per molecule.

14. A process according to claim 1 wherein said hydrocarbon liquid is propylene tetramer.

1S. A process according to claim 1 wherein said hydrocarbon liquid consists essentially of aromatic hydrocarbons of 9 to l0 carbon atoms per molecule.

i6. A process according to claim 1 wherein said hydrocarbon .liquid consists essentially of naphthenes of 9 t0 l0 carbon atoms per molecule.

17. A process for extracting Water from ibrine Comprising:

(a) bringing into contact with one another in an extraction zone at an elevated temperature and a pressure sulicient to maintain liquidI brine in said extraction zone, hot brine and a hot organic liquid characterized by the ability to extract more water at a high temperature than at a lower temperature there- -by extracting substantially pure water into said organic liquid and forming a complex therewith immiscible with said brine;

( b) separating said complex from residual brine;

(c) decomposing said complex into a water phase and an organic liquid phase by reducing the temperature of said complex by at least 50 F.;

(d) and separating said water phase from said organic liquid phase.

18. A process in accordance with claim 17 wherein said elevated temperature is above 500 F. and said pressure is above 1000 p.s.i.g.

19. A process in accordance with claim 18, comprising reheating said organic liquid phase and recycling said organic phase in a liquid condition back into contact with brine in said extraction zone, for further extraction of water.

References Cited by the Examiner UNITED STATES PATENTS 10/1942 Harrington 208-311 l/1961 Baniel 210-21 UNITED STATES` PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,316,172 April 2s, 1967 Howard V. Hess It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below Column 3, line 33, for H.200" read Z000 Signed and sealed this 21st day of November 1967.

(SEAL) Attest:

EDWARD J BRENNER Edward M. Fletcher, Jr.

Commissioner of Patents Attesting Officer 

1. A PROCESS FOR EXTRACTING WATER FROM BRINE COMPRISING BRINGING INTO CONTACT WITH ONE ANOTHER IN AN EXTRACTION ZONE HOT BRINE AND A HOT HYDROCARBON LIQUID CONSISTING ESSENTIALLY OF HYDROCARBONS CONTAINING NOT LESS THAN 6 AND NOT MORE THAN 30 CARBON ATOMS PER MOLECULE CHARACTERIZED BY THE ABILITY TO EXTRACT MORE WATER AT A HIGH TEMPERATURE THAN AT A LOWER TEMPERATURE THEREBY EXTRACTING WATER INTO SAID HYDROCARBON LIQUID AND FORMING A COMPLEX THEREWITH, REMOVING SAID COMPLEX FROM CONTACT WITH RESIDUAL BRINE, COOLING SAID COMPLEX TO FORM A WATER PHASE AND HYDROCARBON PHASE, AND SEPARATING SAID WATER PHASE FROM SAID HYDROCARBON PHASE. 